Aryloxy-alkacyl-arylenes



Patent/ed Oct. 24, 1944 i y 2,361,32i

Elzllsdu Bont de .Nemours...&Cemn`zmy,L Wil-1 mngton, Del., acorporation of Delaware g o t'ype represented bythefo'rmul'a' y Il tsofv lie invention are aizi'lainedln l mc ac in l d dosasaulf` mandsylforli @Moens/animes., gime amines oladiammesof phenomene nannthaleneand biphenylise ,lhddiamino mood-J ucts are made by reducing the nitrogroups of the end nigga phenyl radicals. rm,

Molje" partcnvleiifly, v` pljodkdopsg'epreseied by the followinggenerallformlae are produced:

" nN-gryl-lY.

@ments dieAAV viasY cooled to 30 C mined by nitrate value, `was 87.7

was maintained at reflux temperature (112114 C.) for 31/2 hours longerand then cooled to 25 C.

The cooled chargewas diluted with 117 parts of Water andwhile keepingthe temperature below C., sodium hydroxide was then slowly added untilthe charge was faintly alkaline to fascina? phenolphthalein papers. Themixture was stirred 10 minutes and filtered. The lter c'ake was timeanddestroying the excess nitrile with sulfamic acid. A spot of thissolution was made on iilter'paper and reacted withl a drop of alkalinel"I-I acid. IThe development l'of a `reci color would indicate thepresence of free amine and an Y incomplete condensation.

. When the test showed the free amine was not present, sodium carbonatewas added to the renitro phenoxy acetylamino) -3 fnitrofbenzene thusproduced was 98.5% pure as'determined by its TiCla value and it meltedat 1771807C.\

34 (4' -amz'no-phenoy-acetylamz'no) -1 benzene A mixture consisting of 1374 parts of'1'(4'nitro phenoxy acetylaminol-'l-initro benzene, 13.7parts of reduced nickel'catalyst and 21.8 parts of anhydrousmethanol'was charged into an auto# clave and the air was flushed' outwith hydrogen. The auto'clave'wasI closed and the charge was heated' to90-100 C.' and'sti'rred underv 5 00 lbs/sq.r in. hydrogen' pressureyuntil no more hydrogen was absorbed. The charge'Wa's-kept intlieautoclave at'901,00 C. under 500 lbs/sq. in.

, hydrogen pressure for 1/2A hour longenfthen cooled to -35 C; andfiltered. The filtrate was slowly added to 1335 parts of cold waterwhich" had been made slightly'alkaline to phenollph'thalein paper whilstkeeping'fthe mixture below 20 C. 'I'his mixture was stirred l-minutesandltered. The press cake was thoroughlywashed and dried in an air dryer at30 C. The melting point of the product was 93-95 C. andvits purity, asdeter isrepresented bythe formula v o -v i mit--o-om--nNQ NH2 y yYExaminar: II 1,3-dz'(4initro-phenoy-cetyiamino)' benzene- 4-sulfom'cacid A solution was madev by dissolving 188 parts of1,3-diamino-benzenefifsulionic acid in 2000 parts of wateru at `1020 C.which had been made Y .l filtration and the press cake :was washed withThe product y.

faintly ,alkaline with approximately parts of sodium carbonate. Anothersolution was made by dissolving fiilnparts of 4-nitrophenoxyacetylchloride .in approximately 2000 parts `o11,2-dichloroethane. Enough yoi thelatter solution was slowly added tothe firstfsolutionv overa period `of 1, to 2 hours to provide nearlyenough 4-nitrophenoXy-aceftyl`i chloride to combine with the1,3!diar'ninolbenzene sulfonic acid.; During `,this time, good agitationand a temperature of 10- 20 C. were maintained'fandsodium carbonate was`slowly, added when needed to keepthe mixture faintlyalkaline'.tophenol-phthalein paper. The mixture was agitated at 10-20 C.for 3 hours longer.v 'Small portions of the solution of4-nitrophenoxy-acetylchloride were then added with subsequent-stirringand the same conditions ofV temperature and alkalinity until themixture' containedlno free-amino compound'asindicated by test. i. I'-fj- The testy for'the presence of `free ami'nosc'om-v pound was madebytaking-rv a small `'sampleof the reaction mixture, cooling to 0{-5-C.,acidifying t'sCongo 'redwithhydrochlor'ic acid, adding a small amount of*'so'diun'i` nitrite,l stirringa'. shortv actionmixture to giveadistinct alkaline reaction to plienolphthalein'I paper and thisalkalinity was maintained for 15 minutes. The solids were iilteredoilland `rthe lter cake was Washed with Water and dried in an oven at75-80 C. The purity of the 1,3-di(4-nitro-phenoxy-acetylamino)-benzene-i-sulfonic acid thus obtained as determined by titrating thenitro groups with titanium trichloridesolution'was 91.2%.

To avmixture-of 1000 parts of water, 250'parts' of fine iron borings andl15 parts o'f acetic acid Whichwasheated to C., the above `preparednitrobody was slowly added vduring "a'period of about'tlo'ree hourswhile rgood Aagitation and a The ltratewascooled to-25.30 C; andrendered slightly acid' to Congo 'fred papers ywith sul# furic acid andthen cooled to 20 C. The precipitated L3 .-di(4' amino'- phenoxyacetylamino) -benzene-l-sulfonic acid was separated by about 200 partsof water and dried in an air dryer at.50 C. The purity of the product asdetermined byI ntritevalue was ,66%r-fs,

Theproduct is -represented Eby the formula:

l o n,

nlNGocHfo-nNQsom NH-o-ongo NH, 3

ExAMPLs III A solution was made by dissolving parts of4-nitro-phenoxy-acetyl chloride in approximately 665 parts of ethylenedichloride and warmingtoy 70 C. The solution was cooled to 20 C. and asolution composed of 30 parts of 1,3-diamino benzene. 26 parts of sodiumhydroxide and 210 parts of water was slowly added whilst maintaining atemperature of 10-20- ;C. and phenolphthalein alkalinity as directedinthe preceding example. The mixture was stirred 3 hours after theaddition of the chloride Isolution.

The resulting slurry was illtered and the iilter cake was washed wit papproximately 300 parts of water at 20 C. and then with 200 parts ofwater zweite-ai? which had been distinctly acid to Congo red paper witha small amount of hydrochloric acid. The 1,3 di'(4'nitro-phenoxy-acetylamino) -benzene thus obtained was dried in an airdryer at 65 C. The dried product was 96.8% pure and melted at 259 C.

" 1,3412' (4aminophenomyacetyl amino) -benzene A charge composed of 150parts of 1,3di(4' and the'v product Was dried virr'a vacuum oven Vat '60C. Thev 'dii'e'd'pi'dct Was-a 'light powd nitrate until it was alkalineto phenoiphthain papers and the precipitated diamino compound wasfiltered oi. The lter cake was Washed-With 200 parts of an aqueoussolution containing 1% sodiur carbonate and 1% sodium hydrosuldewhicnnreited at 15P-153 c. and had a purity of about'99% as determinedby nitrite value.

' The' reduct is 're resented Vb the formula:nitro-phenoxy-acetylamino)benzene, 15 parts of n.) y p p yf l nickelcatalyst and 250 parts of ethanol in a closed autoclave, from which theair had been flushed H1N0CH2C"NH out with hydrogen gas, was heated to 90C. and Li L stirred under 500 lbs./sq. in. hydrogen pressure 1. NH(ECHzQQNHf, until no more hydrogen was absorbed. l'I'he 5 i O charge washeld in the autoclave at 90 C. with The; following (compounds which arerepreagitation for one-half hour longer and then sented-why formulaewere Iprepared by methods l cooled to 253D C. The charge was removedsimilar tqtnos'e described in the foregoing exf from the autoclave andmade acid to Congo red 20 amples". The purity of the nitro compounds waspaper by adding hydrochloric acid. The mixture determined by TitClsvalue and the purity of the was stirred until the amine was dissolvedand amino compounds was determined by nitrite claried by filtering.Ammonia was added to the value.

Example Formula y Lgeglg Purity v I i y C. Percent OCH: (u) iv; @NGOanim-ENQ' izzr sim- (l 00H: Hna-O o Gwenn-@ sii/i100 74.3

I NH:

(d OCHA v om@ -oHlo-HNQ-Nm 21e-217' 60.7

00H3 ...NGOCHlLHNQm l CH:

f 00H, vI...' ..-.y o'nN-OCHQNNQ, i 1 '179i 97.0

(CH: HNGOCLNQh-; 9a 19.6

OCE; No: vn. olNocnlg-N@ v207i I 96.4

oCH Nm' HQNoCm-HN 'l Ga' vm ozNG-oonlcni-HNQ 214? 99.3

I No.

, CH: HNGQCEM@ i NH,

, aration of azo dyes.

Example Formula Llglg Purity C. Per een! CH: i Xvn olN-O-ocmc-HN No. 17598.1

CHI i 1am-Oo omc-41N NH, oo 01.1

No, i Xvrn-.--- ocHlo-HN-ONO, 231l 90.0

i o CHlC-HN-ONH, 13o-132 As illustrations of other nitro acid halideswhich can be used in making other compounds of the invention instead ofthose enumerated in the foregoing examples are mentioned 4methyl2nitrophenoXy-acetyl chloride, beta(4nitro phenoxy) propionylchloride, alpha 4 nitrophenoxy) -propionyl chloride, alpha(3nitrophenoxy)nbutyry1 bromide, 2,4-dimethyl-5-nitrophenoxy-acetyl chloride,2,4-dichloro-5-nitro-v phenoxy acetyl chloride, alpha(4 nitrophebenzidine-diglycolic acid, 1,3-diamino-4-chlorobenzene, dianisidine,benzidine, tolidine, 3,3'di methyl-2,2'-dichloro-benzidine, methoxybenzidine, 3,3' dimethoxy 6,6'di chloro benzidine, 1,4 diaminonaphthalene- 6carboxylic acid, l-amino-l-nitro-naphthalene- 6sulfonicacid, 1-amino-4-nitro-naphthalene-'lsulfonic acid,1,4diamino-naphthalene-6-sulfonic acid, 2-amino-5-nitro-phenoxy-aceticacid, 2,5-diamino-phenoxy-acetic acid, 2-amino-4-nitro phenoxy aceticacid, 4 nitro 2 ethylaniline, 1,4-diamino-2-isopropyl-benzene and 4-nitro-2-isoamyl aniline. l

The new compounds can be used for various purposes. Besides being usefulas intermediates from which other compounds can be made, many of theamino derivatives can be used as azo dye coupling components. The aminoderivatives are also valuable as tetrazo bases for the prep- Variousdyes made with such tetrazo bases have been found to have surprisinglybright shades and other desirable properties desired in azo dyes.

As indicated in the foregoing examples, toluene is a suitable inertorganic solvent in the condensation but other inert organic solvents canbe used, such as ethylene-dchloride, ortho-dichlorobenzene, chloroform,carbon tetrachloride and benzene, due regard being had to the knownlimitations of such inert solvents. By inert organic solvent is meant anorganic solvent which will form a solution with the material to bereacted and Whichlwill not be acted upon so as to impair thecondensation or reduction product to be manufactured. In the catalyticreduction, methanol is indicated as a suitable inert organic solvent butothers can be used, such as hexane, benzene, ethanol, dioxan andethylene glycol. Any of the nickel hydrogenation catalysts, such asreduced nickel on an inert support orRaney" nickel catalyst aresuitable.

Still other modifications in the reduction of the nitro groups can bemade such as the reduction of the nitro groups by the action of variousalkali metal suldes in ammoniacal reducing media. Thus manymodifications can be made in the methods of producing the describedcompounds with respect to the temperature and proportions of thereaction media, the inert solvent. the addition' rates,'the reducingagent, pressures and the like, Without departing from the invention.

From the foregoing disclosure it will be recognized that the inventionis susceptible of modication Without departing from the spirit and scopethereof and itis to be understood that the invention is not restrictedto the specific illustrations thereof herein set forth.

I claim:

The compound represented by the'formula CHILEs E. SPARKS.

Certiicate of Correction Patent No. 2,361,327. October 24, 1944.

-CHILES E. SPARKS It is hereby certified that errors appear lirl-,theprinted specification of the above lnumbered patent requiring correctionas follows; Page 2, second column, line 1, for

nitrilei read nitrite; page 3, second column, line 12, for that portionof the formula reading p Y mNOw' read 15m-O o page 4, Example XII, forthat portion of the formula reading and that the said Letters Patentshould be read With these corrections therein that the same may conformtothe recordof the case in the Patent Office.

Signed and sealed this 23rd day of January, A. D. 1945.

[SEAL] LESLIE FRAZER,

Acting Commissioner of Patents.

